The present invention relates to a propylene polymer, a propylene block copolymer and process for the preparation thereof, and a propylene polymer composition comprising the propylene polymer or the propylene block copolymer and a stabilizer. More particularly, the invention relates to a propylene polymer having a high crystallinity, a high stereoregularity and an extremely long mesochain (continuous propylene units wherein directions of xcex1-methyl carbons are the same as each other), a propylene block copolymer containing a crystalline propylene portion having a high crystallinity, a high stereoregularity and an extremely long mesochain, and a propylene polymer composition comprising the above propylene polymer or propylene block copolymer and an specific stabilizer.
It has been well known that polyolefins such as crystalline polypropylene are obtained by polymerizing olefins in the presence of so-called Ziegler-Natta catalyst which comprises a compound of a transition metal of Group IV to Group VI in the periodic table and an organometallic compound of a metal of Group I to Group III of the periodic table. Recently, there have been made studies on a process in which crystalline polyolefins of high stereoregularity can be obtained with high polymerization activity using such catalysts as mentioned above.
For example, Japanese Patent Laid-Open Publications No. 209207/1986, No. 104810/1987, No. 104811/1987, No. 104812/1987, No. 104813/1987, No. 311106/1989, No. 318011/1989 and No. 166104/1990 disclose that polyolefins of high stereoregularity can be obtained with high polymerization activity by polymerizing olefins in the presence of a catalyst formed from a titanium-containing sold catalyst component which contains titanium, magnesium, halogen and an electron donor, an organoaluminum compound and an electron donor.
The present applicant has also made a number of proposals with respect to a catalyst for olefin polymerization and an olefin polymerization process by which crystalline polyolefin of high stereoregularity can be obtained with high polymerization activity, as described in, for example, Japanese Patent Laid-Open Publications No. 108385/1975, No. 126590/1975, No. 20297/1976, No. 28189/1976, No. 64586/1976, No. 92885/1976, No. 133625/1976, No. 87489/1977, No. 100596/1977, No. 147688/1977, No. 104593/1977, No. 2580/1978, No. 40093/1978, No. 40094/1978, No. 43094/1978, No. 135102/1980, No. 135103/1980, No. 152710/1980, No. 811/1981, No. 11908/1981, No. 18606/1981, No. 83006/1983, No. 138705/1983, No. 138706/1983, No. 138707/1983, No. 138708/1983, No. 138709/1983, No. 138710/1983, No. 138715/1983, No. 138720/1983, No. 138721/1983, No. 215408/1983, No. 47210/1984, No. 117508/1984, No. 117509/1984, No. 207904/1984, No. 206410/1984, No. 206408/1984, No. 206407/1984, No. 69815/1986, No. 69821/1986, No. 69822/1986, No. 69823/1986, No. 22806/1988, No. 95208/1988, No. 199702/1988, No. 199703/1988, No. 202603/1988, No. 202604/1988, No. 223008/1988, No. 223009/1988, No. 264609/1988, No. 87610/1989, No. 156305/1989, No. 77407/1990, No. 84404/1990, No. 229807/1990, No. 229806/1990 and No. 229805/1990.
Crystalline polypropylene is rigid and usually has a high heat distortion temperature, a high melting point and a high crystallization temperature, and hence it shows excellent properties such as high heat resistance, high crystallization speed and high transparency. Accordingly, crystalline polypropylene has been applied to various uses such as containers and films. Since rigidity and heat resistance of polypropylene are enhanced with increase of crystallinity, polypropylene having high crystallinity can be applied to such uses as require higher rigidity and higher heat resistance. Further, in the conventional uses, a product formed from the polypropylene can be made thin or an amount of a filler to be added can be reduced, that is, weight-saving can be attained.
A propylene block copolymer usually comprises a crystalline polypropylene portion and a non-crystalline polymer portion, and has excellent properties such as lightweight and good balance between rigidity, a heat distortion temperature and impact resistance. Accordingly, the propylene block copolymer has been applied to various uses such as structural materials for containers and electrical appliances and automotive interior trims. Since rigidity and heat resistance of a propylene block copolymer are enhanced with increase of crystallinity of the crystalline polypropylene portion, a propylene block copolymer containing a polypropylene portion of high crystallinity can be applied to such uses as require higher rigidity and higher heat resistance. Further, in the conventional uses, a product formed from the the propylene block copolymer can be made thin or an amount of a filler to be added can be reduced, that is, weight-saving can be attained.
The crystallinity of crystalline polypropylene has been conventionally heightened by a method of adding a nucleating agent or other method, but the conventional crystalline polypropylene has an isotactic pentad value (pentad isotacticity) by the NMR measurement of about 90 to 95%, and the improvement of the rigidity and the heat resistance is limited to a certain extent. Accordingly, there have been keenly desired the advent of a crystalline polypropylene having a prominently high isotactic pentad value, namely a crystalline polypropylene having a high stereoregularity, and the advent of a propylene block copolymer containing a crystalline polypropylene portion having a prominently high isotactic pentad value, namely a propylene block copolymer containing a crystalline polypropylene portion having a high stereoregularity.
Films made of the conventional crystalline polypropylene are not always sufficient in moisture resistance, and hence the advent of a crystalline polypropylene excellent in the moisture resistance as well as in the rigidity and the heat resistance has been also desired.
In the case of molding the above-mentioned crystalline polypropylene, moldability of a resin is improved when a melt viscosity of the resin is low, and hence a resin temperature is generally elevated to lower the melt viscosity of the resin. However, if the resin is molded at a high temperature, the resin tends to be thermally decomposed or deteriorated to sometimes cause various problems such as coloring of the resulting molded product, occurrence of cracks, lowering of long-term heat stability and weathering resistance, and reduction of rigidity and heat resistance.
Further, sheets or films made of the conventional crystalline polypropylene are not always sufficient in the moisture resistance in some uses, and accordingly the advent of a crystalline polypropylene excellent in the moisture resistance as well as in the rigidity and the heat resistance has been desired.
The present inventors have earnestly studied to solve the above-mentioned problems, and as a result, they have found that a propylene polymer composition comprising a propylene polymer (or a propylene block copolymer) which has a much higher stereoregularity than a conventional one and an extremely long mesochain and a specific stabilizer shows high rigidity, high heat resistance and high moisture resistance, and moreover is excellent in heat stability during the molding stage, long-term heat stability of the molded product and weathering resistance thereof as compared with a conventional crystalline polypropylene. Thus, the present invention has been accomplished.
It is an object of the present invention to provide a propylene polymer which is excellent in rigidity, heat resistance and moisture resistance and a process for preparing said propylene polymer.
It is another object of the present invention to provide a propylene block copolymer which is well balanced between rigidity, heat resistance and impact resistance and a process for preparing said propylene block copolymer.
It is a further object of the present invention to provide a propylene polymer composition comprising the above-mentioned propylene polymer or propylene block copolymer and a stabilizer, which has excellent properties of the propylene polymer or the propylene block copolymer and is capable of forming a molded product excellent in heat stability during the molding stage, long-term heat stability and weathering resistance.
The propylene polymer of the present invention is a propylene polymer having such properties that:
a melt flow rate (MFR) of said polymer at 230xc2x0 C. under a load of 2.16 kg is in the range of 0.1 to 500 g/10 min,
a pentad isotacticity [M5] obtained from the following formula (1) using absorption intensity [Pmmmm] and [Pw] in a 13C-NMR spectrum of a boiled heptane-insoluble component contained in said polymer is in the range of 0.970 to 0.995,
a pentad tacticity [M3] obtained from the following formula (2) using absorption intensity [Pmmrm], [Pmrmr], [Pmrrr], [Prmrr], [Prmmr], [Prrrr] and [Pw] in a 13C-NMR spectrum of a boiled heptane-insoluble component contained in said polymer is in the range of 0.0020 to 0.0050, and
a crystallinity of a boiled heptane-insoluble component contained in said polymer is not less than 60%;                               [                      M            5                    ]                =                              [            Pmmmm            ]                                [            Pw            ]                                              (        1        )            
wherein
[Pmmmm] is absorption intensity of methyl groups present in the third unit among continuous five propylene units which are bonded to each other with meso form, and
[Pw] is absorption intensity of all methyl groups in a propylene unit;                               [                      M            3                    ]                =                                            [              Pmmrm              ]                        +                          [              Pmrmr              ]                        +                          [              Pmrrr              ]                        +                          [              Prmrr              ]                        +                          
                        ⁢                          xe2x80x83                        ⁢                          [              Prmmr              ]                        +                          [              Prrrr              ]                                            [            Pw            ]                                              (        2        )            
xe2x80x83wherein
[Pmmrm] is absorption intensity of methyl groups present in the third unit among continuous five propylene units represented by ┘┘┘┐┐ in which ┘ and ┐ are each a propylene unit,
[Pmrmr] is absorption intensity of methyl groups present in the third unit among continuous five propylene units represented by ┘┘┐┐┘ in which ┘ and ┐ are each a propylene unit,
[Pmrrr] is absorption intensity of methyl groups present in the third unit among continuous five propylene units represented by ┘┘┐┘┐ in which ┘ and ┐ are each a propylene unit,
[Prmrr] is absorption intensity of methyl groups present in the third unit among continuous five propylene units represented by ┐┘┘┐┘ in which ┘ and ┐ are each a propylene unit,
[Prmmr] is absorption intensity of methyl groups present in the third unit among continuous five propylene units represented by ┐┘┘┘┐ in which ┘ and ┐ are each a propylene unit,
[Prrrr] is absorption intensity of methyl groups present in the third unit among continuous five propylene units represented by ┘┐┘┐┘ in which ┘ and ┐ are each a propylene unit, and
[Pw] is absorption intensity of all methyl groups in a propylene unit.
The propylene polymer of the invention desirably contains 10-10,000 ppm of polymer comprising constituent units derived from a compound represented by the following formula (i) or (ii):
H2Cxe2x95x90CHxe2x80x94Xxe2x80x83xe2x80x83(i)
H2Cxe2x95x90CHxe2x80x94CH2xe2x80x94Xxe2x80x83xe2x80x83(ii)
wherein X is a cycloalkyl group, an aryl group or 
M is carbon or silicon, R1 and R2 are each a hydrocarbon group, and R3 is hydrogen or a hydrocarbon group.
The propylene block copolymer of the present invention is a propylene block copolymer having such properties that:
a melt flow rate (MFR) of said copolymer at 230xc2x0 C. under a load of 2.16 kg is in the range of 0.1 to 500 g/10 min,
a pentad isotacticity [M5] obtained from the following formula (1A) using absorption intensity [Pmmmm], [Pw], [Sxcex1xcex3], [Sxcex1xcex4+] and [Txcex4+xcex4+] in a 13C-NMR spectrum of a boiled heptane-insoluble component contained in said copolymer is in the range of 0.970 to 0.995,
a pentad tacticity [M3] obtained from the following formula (2A) using absorption intensity [Pmmrm], [Pmrmr], [Pmrrr], [Prmrr], [Prmmr], [Prrrr], [Pw], [Sxcex1xcex3], [Sxcex1xcex4+] and [Txcex4+xcex4+] in a 13C-NMR spectrum of a boiled heptane-insoluble component contained in said copolymer is in the range of 0.0020 to 0.0050, and
a crystallinity of a boiled heptane-insoluble component contained in said copolymer is not less than 60%                               [                      M            5                    ]                =                              [            Pmmmm            ]                                              [              Pw              ]                        -                          2              ⁢                              (                                                      [                                          S                      ⁢                                              xe2x80x83                                            ⁢                      α                      ⁢                                              xe2x80x83                                            ⁢                      γ                                        ]                                    +                                      [                                          S                      ⁢                                              xe2x80x83                                            ⁢                                              αδ                        +                                                              ]                                                  )                                      +                          3              ⁡                              [                                  T                  ⁢                                      xe2x80x83                                    ⁢                                      δ                    +                                    ⁢                                      δ                    +                                                  ]                                                                        (1A)            
wherein
[Pmmmm] and [Pw] have the same meanings as defined in the aforementioned formula (1),
[Sxcex1xcex3] is absorption intensity of such secondary carbons that are present in a main chain and out of two kinds of tertiary carbons positioned nearest to said secondary carbons one is situated at the xcex1 position and the other is situated at the xcex3 position,
[Sxcex1xcex4+] is absorption intensity of such secondary carbons that are present in a main chain and out of two kinds of tertiary carbons positioned nearest to said secondary carbons one is situated at the xcex1 position and the other is situated at the xcex4 position or farther than the xcex4 position, and
[Txcex4+xcex4+] is absorption intensity of such tertiary carbons that are present in a main chain and out of two kinds of tertiary carbons positioned nearest to said tertiary carbons one is situated at the xcex4 position or farther than the xcex4 position and the other is also situated at the xcex4 position or farther than the xcex4 position;                               [                      M            3                    ]                =                                            [              Pmmrm              ]                        +                          [              Pmrmr              ]                        +                          [              Pmrrr              ]                        +                          [              Prmrr              ]                        +                          
                        ⁢                          xe2x80x83                        ⁢                          [              Prmmr              ]                        +                          [              Prrrr              ]                                                          [              Pw              ]                        -                          2              ⁢                              (                                                      [                                          S                      ⁢                                              xe2x80x83                                            ⁢                      α                      ⁢                                              xe2x80x83                                            ⁢                      γ                                        ]                                    +                                      [                                          S                      ⁢                                              xe2x80x83                                            ⁢                                              αδ                        +                                                              ]                                                  )                                      +                          3              ⁡                              [                                  T                  ⁢                                      xe2x80x83                                    ⁢                                      δ                    +                                    ⁢                                      δ                    +                                                  ]                                                                        (2A)            
wherein
[Pmmrm], [Pmrmr], [Pmrrr], [Prmrr], [Prmmr], [Prrrr] and [Pw] have the same meanings as defined in the aforementioned formula (2), and
[Sxcex1xcex3], [Sxcex1xcex4+] and [Txcex4+xcex4+] have the same meanings as defined in the above-mentioned formula (1A).
The propylene block copolymer of the invention desirably contains 10-10,000 ppm of polymer comprising constituent units derived from a compound represented by the aforementioned formula (i) or (ii).
The first process for preparing a propylene polymer according to the present invention is a process for preparing a propylene polymer having a crystallinity of not less than 60%, which comprises polymerizing propylene in the presence of a catalyst for olefin polymerization comprising:
[I] a prepolymerized catalyst obtained by prepolymerizing at least one reactive monomer represented by the following formula (i) or (ii) using (a) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components and (b) an organometallic catalyst component, said reactive monomer being prepolymerized in an amount of 0.1 to 1,000 g per 1 g of the solid titanium catalyst component (a);
H2Cxe2x95x90CHxe2x80x94Xxe2x80x83xe2x80x83(i)
H2Cxe2x95x90CHxe2x80x94CH2xe2x80x94Xxe2x80x83xe2x80x83(ii)
wherein X is a cycloalkyl group, an aryl group or 
M is carbon or silicon, R1 and R2 are each a hydrocarbon group, and R3 is hydrogen or a hydrocarbon group;
[II] the organometallic catalyst component (b); and
[III] a silicon compound represented by the following formula (iii) or a compound having at least two ether linkages existing via plurality of atoms:
Ranxe2x80x94Sixe2x80x94(ORb)4xe2x88x92nxe2x80x83xe2x80x83(iii)
wherein, n is 1, 2 or 3; when n is 1, Ra is a secondary or a tertiary hydrocarbon group; when n is 2 or 3, at least one of Ra is a secondary or a tertiary hydrocarbon group, Ra may be the same or different, and Rb is a hydrocarbon group of 1 to 4 carbon atoms; and when 4xe2x88x92n is 2 or 3, Rb may be the same or different;
in said process, propylene being polymerized in an amount of 3,000 to 1,000,000 g per 1 g of the solid titanium catalyst component (a) contained in the prepolymerized catalyst.
The second process for preparing a propylene polymer according to the present invention is a process which comprises preparing a propylene polymer having an intrinsic viscosity [xcex7] of 3 to 40 dl/g in an amount of 0.1 to 55% by weight based on the amount of the resulting polymer using one or more polymerizers out of two or more polymerizers and then further preparing a propylene polymer using the residual polymerizers, in the presence of a catalyst for olefin polymerization comprising:
[I] a prepolymerized catalyst obtained by prepolymerizing at least one reactive monomer represented by the following formula (i) or (ii) using (a) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components and (b) an organometallic catalyst component, said reactive monomer being prepolymerized in an amount of 0.1 to 1,000 g per 1 g of the solid titanium catalyst component (a);
H2Cxe2x95x90CHxe2x80x94Xxe2x80x83xe2x80x83(i)
H2Cxe2x95x90CHxe2x80x94CH2xe2x80x94Xxe2x80x83xe2x80x83(ii)
wherein X is a cycloalkyl group, an aryl group or 
M is carbon or silicon, R1 and R2 are each a hydrocarbon group, and R3 is hydrogen or a hydrocarbon group;
[II] the organometallic catalyst component (b); and
[III] a silicon compound represented by the following formula (iii) or a compound having at least two ether linkages existing via plurality of atoms:
Ranxe2x80x94Sixe2x80x94(ORb)4xe2x88x92nxe2x80x83xe2x80x83(iii)
wherein, n is 1, 2 or 3; when n is 1, Ra is a secondary or a tertiary hydrocarbon group; when n is 2 or 3, at least one of Ra is a secondary or a tertiary hydrocarbon group, Ra may be the same or different, and Rb is a hydrocarbon group of 1 to 4 carbon atoms; and when 4xe2x88x92n is 2 or 3, Rb may be the same or different;
the propylene polymer obtained by said process satisfying the following requisites:
(a) a crystallinity of said polymer is not less than 60%,
(b) a melt flow rate of said polymer at 230xc2x0 C. is in the range of 0.1 to 500 g/10 min, and
(c) said polymer is a propylene polymer obtained by polymerizing propylene in an amount of 3,000 to 100,000 g per 1 g of the solid titanium catalyst component (a).
The process for preparing a propylene block copolymer according to the present invention is a process which comprises a first polymerization stage for homopolymerizing propylene or copolymerizing propylene with ethylene and/or xcex1-olefin of 4 to 10 carbon atoms to prepare a crystalline polymer and a second polymerization stage for copolymerizing two or more monomers selected from xcex1-olefin of 2 to 20 carbon atoms to prepare a low-crystalline or non-crystalline copolymer, in the presence of a catalyst for olefin polymerization comprising:
[I] a prepolymerized catalyst obtained by prepolymerizing at least one reactive monomer represented by the following formula (i) or (ii) using (a) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components and (b) an organometallic catalyst component, said reactive monomer being prepolymerized in an amount of 0.1 to 1,000 g per 1 g of the solid titanium catalyst component (a);
H2Cxe2x95x90CHxe2x80x94Xxe2x80x83xe2x80x83(i)
H2Cxe2x95x90CHxe2x80x94CH2xe2x80x94Xxe2x80x83xe2x80x83(ii)
wherein X is a cycloalkyl group, an aryl group or 
M is carbon or silicon, R1 and R2 are each a hydrocarbon group, and R3 is hydrogen or a hydrocarbon group;
[II] the organometallic catalyst component (b); and
(III) a silicon compound represented by the following formula (iii) or a compound having at least two ether linkages existing via plurality of atoms:
Ranxe2x80x94Sixe2x80x94(ORb)4xe2x88x92nxe2x80x83xe2x80x83(iii)
wherein, n is 1, 2 or 3; when n is 1, Ra is a secondary or a tertiary hydrocarbon group; when n is 2 or 3, at least one of Ra is a secondary or a tertiary hydrocarbon group, Ra may be the same or different, and Rb is a hydrocarbon group of 1 to 4 carbon atoms; and when 4xe2x88x92n is 2 or 3, Rb may be the same or different.
The first propylene polymer composition of the present invention comprises:
[A1] a propylene polymer having such properties that
melt flow rate (MFR) of said polymer at 230xc2x0 C. under a load of 2.16 kg is in the range of 0.1 to 500 g/10 min,
a pentad isotacticity [M5] obtained from the aforesaid formula (1) using absorption intensity [Pmmmm] and [Pw] in a 13C-NMR spectrum of a boiled heptane-insoluble component contained in said polymer is in the range of 0.970 to 0.995,
a pentad tacticity [M3] obtained from the aforesaid formula (2) using absorption intensity [Pmmrm], [Pmrmr], [Pmrrr], [Prmrr], [Prmmr], [Prrrr] and [Pw] in a 13C-NMR spectrum of a boiled heptane-insoluble component contained in said polymer is in the range of 0.0020 to 0.0050, and
a crystallinity of a boiled heptane-insoluble component contained in said polymer is not less than 60%; and
[B] a phenol type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene polymer.
The second propylene polymer composition of the present invention comprises:
[A1] the above mentioned propylene polymer,
[B] a phenol type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene polymer; and
at least one compound selected from the group consisting of [C] an organophosphite type stabilizer, [D] a thioether type stabilizer, [E] a hindered amine type stabilizer and [F] a metallic salt of a higher aliphatic acid in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene polymer.
The third propylene polymer composition of the present invention comprises:
[A1] the above-mentioned propylene polymer, and
[C] an organophosphite type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene polymer.
The fourth propylene polymer composition of the present invention comprises:
[A1] the above-mentioned propylene polymer,
[C] an organophosphite type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene polymer, and
at least one compound selected from the group consisting of [D] a thioether type stabilizer, [E] a hindered amine type stabilizer and [F] a metallic salt of a higher aliphatic acid in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene polymer.
The fifth propylene polymer composition of the present invention comprises:
[A1] the above-mentioned propylene polymer, and
[D] a thioether type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene polymer.
The sixth propylene polymer composition of the present invention comprises:
[A1] the above-mentioned propylene polymer,
[D] a thioether type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene polymer, and
at least one compound selected from the group consisting of [E] a hindered amine type stabilizer and [F] a metallic salt of a higher aliphatic acid in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene polymer.
The seventh propylene polymer composition of the present invention comprises:
[A1] the above-mentioned propylene polymer, and
[E] a hindered amine type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene polymer.
The eighth propylene polymer composition of the present invention comprises:
[A1] the above-mentioned propylene polymer,
[E] a hindered amine type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene polymer, and
[F] a metallic salt of a higher aliphatic acid in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene polymer.
The ninth propylene polymer composition of the present invention comprises:
[A1] the above-mentioned propylene polymer, and
[F] a metallic salt of a higher aliphatic acid in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene polymer.
The propylene polymer used in each of the first to ninth propylene polymer compositions of the invention preferably contains 10-10,000 ppm of polymer comprising constituent units derived from a compound represented by the aforesaid formula (i) or (ii).
Such propylene polymer compositions as described above have properties of the propylene polymer and is excellent. in heat stability during the molding stage, long-term heat stability and weathering resistance.
The tenth propylene polymer composition of the present invention comprises:
[A2] a propylene block copolymer having such properties that
a melt flow rate (MFR) of said copolymer at 230xc2x0 C. under a load of 2.16 kg is in the range of 0.1 to 500 g/10 min,
a pentad isotacticity [M5] obtained from the aforesaid formula (1A) using absorption intensity [Pmmmm], [Pw], [Sxcex1xcex3], [Sxcex1xcex4+] and [Txcex4+xcex4+] in a 13C-NMR spectrum of a boiled heptane-insoluble component contained in said copolymer is in the range of 0.970 to 0.995,
a pentad tacticity [M5] obtained from the aforesaid formula (2A) using absorption intensity [Pmmrm], [Pmrmr], [Pmrrr], [Prmrr], [Prmmr], [Prrrr], [Pw], [Sxcex1xcex3], [Sxcex1xcex4+] and [Txcex4+xcex4+] in a 13C-NMR spectrum of a boiled heptane-insoluble component contained in said copolymer is in the range of 0.0020 to 0.0050, and
a crystallinity of a boiled heptane-insoluble component contained in said copolymer is not less than 60%, and
[B] a phenol type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene block copolymer.
The eleventh propylene polymer composition of the present invention comprises:
[A2] the above-mentioned propylene block copolymer,
[B] a phenol type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene block copolymer; and
at least one compound selected from the group consisting of [C] an organophosphite type stabilizer, [D] a thioether type stabilizer, [E] a hindered amine type stabilizer and [F] a metallic salt of a higher aliphatic acid in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene block copolymer.
The twelfth propylene polymer composition of the present invention comprises:
[A2] the above-mentioned propylene block copolymer, and
[C] an organophosphite type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene block copolymer.
The thirteenth propylene polymer composition of the present invention comprises:
[A2] the above-mentioned propylene block copolymer,
[C] an organophosphite type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene block copolymer, and
at least one compound selected from the group consisting of [D] a thioether type stabilizer, [E] a hindered amine type stabilizer and [F] a metallic salt of a higher aliphatic acid in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene block copolymer.
The fourteenth propylene polymer composition of the present invention comprises:
[A2] the above-mentioned propylene block copolymer, and
[D] a thioether type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene block copolymer.
The fifteenth propylene polymer composition of the present invention comprises:
[A2] the above-mentioned propylene block copolymer,
[D] a thioether type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene block copolymer, and
at least one compound selected from the group consisting of [E] a hindered amine type stabilizer and [F] a metallic salt of a higher aliphatic acid in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene block copolymer.
The sixteenth propylene polymer composition of the present invention comprises:
[A2] the above-mentioned propylene block copolymer, and
[E] a hindered amine type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene block copolymer.
The seventeenth propylene polymer composition of the present invention comprises:
[A2] the above-mentioned propylene block copolymer,
[E] a hindered amine type stabilizer in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene block copolymer, and
[F] a metallic salt of a higher aliphatic acid in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene block copolymer.
The eighteenth propylene polymer composition of the present invention comprises:
[A2] the above-mentioned propylene block copolymer, and
[F] a metallic salt of a higher aliphatic acid in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene block copolymer.
The propylene block copolymer used in each of the tenth to eighteenth propylene polymer compositions of the invention preferably contains 10-10,000 ppm of polymer comprising constituent units derived from a compound represented by the aforesaid formula (i) or (ii).
Such propylene polymer compositions as described above have properties of the propylene polymer and is excellent in heat stability during the molding stage, long-term heat stability and weathering resistance.